Dyestuffs which are complex copper-ammine compounds



Patented Feb. 1 1, 1930 QUNIITED ST -res PATENT OFFICE MRI]! ,HENTBIGHAND MAX HABDTMANN, Q]? .WIESDOBF-ON-THE-RHINE, GER- um, assmnons 'roGENERAL minmn wonxs, me, on NEW roan, N. Y., A con- PORTION OF DELAWAREDYESTUFFS WHICH ARE COMPLEX COPPER-MINE COMPOUNDS Io brewing. Originalapplication filed December 9, 1926, Serial No. 158,723, and in GermanyDecember 12, 1925. Divided and this application iiled October 18, 1927.Serial ll'o. 227,054.

'- The present invention relates to new copper-containing azo dyestuffsand to a process of preparing the'same. More particularly, it

relates to compounds of the general formula:

wherein A represents a disazo. dyestulf molecule containing inortho-position to each azo group, a substituent of the group comprising.the hydroxyl-, the carboxyland the carbonyl groups, X representshydroxyl, a monovalent acid both gzoup suchas -C1,GH;COO-, etc., or stogether representa divalent acid I group such as =SO,, R represents amolecule of the ammonia type or of the aquo (H O) type, but at least oneB. being a molecule of the ammonia type, n represents the number 3 or 5.

Our preferred process for producing our new. compounds consists ineffecting the manufacture ofthe azo dyestuifs'in question,

which may consist, for instance, in diazotizing an aromatic aminecontaining 'a -hy droxyl-, carboxyl-, or a carbonyl group inortho-position to the diazo compound, and coupling the diaz'o compoundthus obtained with any desired coupling component, in the causing awater-soluble copper-aminine compound to react with'the finished azodyestuif.

The chemical constitution of our new complex dyestuffs is not perfectlyknown. From their mode of formation and their chemical behavior theabove given formula seems to be the best possibleone. We wish it to beunderstood that the expression molecules of the ammonia type, as-used inthe specification, and in the claims, includes ammonia as well asmethyl-amine,.ethylenediamine, pyridine, glycocoll, etc. p g

The copper-ammine compounds which we have found useful and tried out inour new process can be exemplified by the following:

tetrammine-cupri sulfate [Cu(NH;) S0 I tetrammine-cupri hydroxyde:

M Q 4] )2; v hexammine-cupri chloride: [Cu(NI-I ]Cltriethylenediamine-cupri sulfate:

ou H2'N -oH2-oH,-NH2 180 triethylenediamine-cupri chloride: I

[Cu (H N-OH CH -NH ,]'Cl in both of which latter formulae theethylenediamine molecule, often represented herein by the symbol en,acts liketwo ammoniav type molecules; hexa pyridine-eupri-bromide: [Cu(GH N).] Br tetra pyridinecupri-acetate: [Cu(C H N)',] (CI-L000; tetraquinoline-cupr -chloride:

' I [Cu(C H N) AC1,

tetra .trimethyl-amine-cupri sulfate:

, tetra monomethylamine cupri sulfate:

Cu: I (NH CH 4 $0,; the glycocoll compound of the formula: o-cdcu 4m n 22 Oug'- '1 7.

v a free amino group.

diethylenediamine-di-aquo-cupri chloride:

The applicability of our invention in new copper-ammino-azo dyestuffs isan exceedingly wide one and permits of numerous variations also in thechoice of the azo dyestufi' components as well asin the procedure ofpromoting the reaction between these components and the copper-amminecomplex compound.

In the case of tetrazo compounds, substituted in ortho position to bothdiazo groups by hydroxyl, carboxyl or carbonyl groups, the disazodyestuffs produced from them react usually with two molecularproportions of a copper-ammine compound.

Our new complex-copper-ammine-azo dye-v stuffs are obtained by ourprocess directly in substantially pure form and can be used as such fordyeing purposes. They are, when made from sulfonated intermediates,usually water soluble, and due to the possibility of applyin our newreaction to a very large ran e o azo dyestufi components, practically151 possible shades and dyeing properties are obtainable and thedyestuffs are liable to be used for all kinds of dyeing purposes.

It goes without saying that this new class of complex copper ammine azodyestuffs comprises also such (1 estuifs which contain hese, whenapplied for instance to the fibre, can be further diazotized and coupledwith any desired coupling compound.

Similarly it is also possible to diazotize on the fibre suitable azodyestuffs containing no copper, but one or more diazotizable aminogroups and to couple same with suitable coupling compounds in thepresence of a copperammine complex, or particularly with such couplingcompounds which, themselves, are capable of forming complexcopper-ammineazo compounds.

In cases where the new copper-ammineazo dyestuffs contain in orthoposition to a 'hydroxyl group a hydrogen atom capable of Hols-Idyestuffs by reduction, our new products yield a cuprous salt, anitrogen base of the ammonia type, usually in form of a salt, theoriginal aromatic amine and an amino derivative of the couplingcompound.

The following examples will further illustrate our invention, the partsbeing by weight:

Example 1.35O parts tetrammine-cuprisulfate: [Cu(NH ]SO +H O dissolvedin cold water are added to an aqueous solution containing 502 parts5-5-dihydroxy-2-2-dinaphthylurea-7-7'-disulfonic acid and 700 parts sodaash. A suspension of the diazo compound obtained in the usual mannerfrom 374 parts Q-amino-naphthalene-3-carboxylic acid is then run intothe above clear solution. The coupling and formation of the complexcupri-ammine-azo dyestuff start immediately and both reactions arequickly completed. The product is salted out by the addition of somesodium chloride, then filtered off and dried. It is soluble in waterwith a bluish-red color and in concentrated sulfuric acid with abluish-violet color. Upon reduction with stannous chloride inhydrochloric acid solution, it is split up into Q-amino-naphthalene-3-carboxylic acid, 6-6-diamino-5-5-dihydroxy 2 2 dinaphthylurea -7 -7disulfonic acid, cuprous chloride and ammonium chloride. It dyes cottonby the usual dyeing methods very fast bluish-red shades. This complexcupri-ammine-azo dyestufi' has most probably the formula:

(OHM-Cu A (on m Ill Ill lll Ill (N a): (NH:)|

wherein A stands for the disazo dyestufi' of the formula:

We have found that two of the NH, molecules attached by auxiliaryvalencies to each of the copper atoms can be replaced, without departingfrom the spirit of our invention, by aquo rest-s (H O). The third NHmolecule is, however, essential for the production of the desiredresult. This is equally true for all complex cupri-ammine-azo dyestufisprepared according to our invention and particularly so for the formulagiven in the examples below.

The soda ash used as neutralizing agent in this example can be replacedby aqueous ammonia with the same result. Dyestuffs of similar propertiesare obtained by substituting the tetrammine-cupri sulfate of thisexample b fate [Cu 0.11m onacoo) 2;

cupri chloride:

ou NH.- .]o12 or diethylene-diamine-diaquo-cupri chloride:

1 tetra-trimethylammine-cupri sulhexammine- (en) standing for anethylene-diamine molecule. The formulae of these dyestuffs arecorrespondingly similar.

Example 2.137 parts Q-amino-benzoic acid are diazotized'in the usualmanner. In the meantime 461 parts 55-dihydroxy-2-2-dinapththylamine-7-7'-disulfonic acid and 7 7 0 parts soda ash aredissolved in 8750 parts water and a solution ofdiethylene-diaminedi-aquo-cupri sulfate of the formula:

(en) standing for an ethylene-diamine molecule, prepared from 490 partscrystalhzed copper sulfate, according to Werner, f. anorg. Chem, vol.21, page 233 (1899), is added. The above diazo solution is then addedwith cooling to this clear bluish solution of the5-5-dihydroxy-2-2'-dinaphthyl- .amine-7-7-disulfonic acid. The reactionmass is heated for some time to 30-40 C. to complete the formation ofthe dyestufi, which is then salted out, filtered off, washed and dried.It has most probably the formula:

(011) Qu n- A Oui (08) v wherein A stands for disazo dyestuif of theformula:

and hydrochloric acid Q-amino-benzoic acid,

Zeitsch.

Qliiigl flgiiilj 6 -6' -diamin0 -5- 5'-dihydroxy-2-2'-dinaphthylamine-7-7-disulfonic acid, cuprous chlorideand ethylene-diamine hydrochloride.

Example 3.--The tetrazo compound obtained from 350 parts4-4-diamino-dipheny1urea-3-3 -dicarboxylic acid is coupled in aceticacid solution with 315 parts Q-phenylamino-5-naphthol-7-sulfonic acid.The solu tion is made distinctly alkaline, after the coupling iscomplete, then an already prepared solution of tetrammine-cupri sulfate,prepared from 700 parts crystallized copper sulfate and about 1340 parts20% aqueous ammonia, and finall a concentrated aqueous solution ofQ-acety -amino-5-hydroxynaphthalene-7-sulfonic acid, are added. Thereaction mass is stirred for some time, the temperature being increasedat the end to about 3040 G.; the dyestuff is then isolated in the usualmanner, and has probably the formula:

( m n): (Bi l1 wherein A stands for the disazo-dye of the formula:

H Qrhm/ OOH NH The so obtained complex cupri-ammine-azo dyestuff dyescotton clear, violet shades of very good fastness to light, alkali andacid. The 2-acetylamino -5-naphthol -7 -sulfonic acid used in thisexample can be replaced by the isomer2-acetylamino-8-naphtho1-6-sulfonic acid or the 1-acetyl-, respectively1-benzoyl-amino-8-naphthol-3-6-disul-fonic acid, complexcupri-ammine-azo dyestuffs having similar roperties and dyeingsimilar'shades are so 0 tamed.

Ewample 4.-33O parts 4-4'-diamino-diphenylurea-3-3'-dicarboxylic acidare tetrazotized and coupled at ordinary temperature with an aqueoussolution of 704 parts 2- henyl amino 5 hydroxynaphthalene-7-sulibnate ofsodium containing 700 parts soda ash and 350 parts tetrammine-cuprisulfate. The complex cupri-ammine-azo dyestufi formed isisolated intheusual manner. It has probably the formula:

dicarboxylic acid, 2-pheny wherein A stands for the diazo dyestufi ofthe formula:

The novel product is soluble in water with a strongly bluish-red and inconcentrated sulfuric acid with a bluish-red color. It dyes cotton fastreddish-violet shades; Reduction with stannous chloride and hydrochloricacid yields 4-4f-diamino-diphenylurea-3-3'-amino-6-aminolflhydroxy-naphthalene-7-sulfonic acid, cuprous chlorideand ammonium chloride. Tetrazotized benzidine 3 3-dicarboxylic acidcoupled with 2 molecular proportions of 1-naphthol-4-sulfonic acid inthe presence of cupn-ammines, such as diethylenediaminedi-aquo-cuprisulfate of the formula:

u so.

New 4 or tetra-mono-methylamino-cupri sulfate:

[ (N .GH.). =so.

produces "cupri-ammine-azo d estufis of similar constitution. It is in aike manner possible to introduce similar azo dyestufi. molecules into ayridine-copper ammine, such as tetra-pyri ne-cupri chloride:

7 [C 1(Cs s 41 2 I tained as follows: 5-nitro-2-amino-benzoic acid iscoupled in alkaline solution with2-phenylamino-5-hydroxynaphthalene-7-sulfonic acid in the presence oftetramminecupri sulfate. The nitro group contained in the so obtainedcupri-ammine-amino-azo complex is then reduced in the well known mannerby means of an alkali sulfide and finally the cupri-ammine-azo complexis treated with, phosgen.

0.1mm 110.1%. NHCaHI N=N: Nnco-Nn-QN=N n c on I 00H n Example 5.242parts 2-amino-benzaldehyde, or the corresponding amount of its anhydroform are diazotized. The diazocompound is run at 5 CL into an aqueoussolution of 461 parts 5-5-dihydroxy-2-v2-dinaphthyl-amine-'Z-7-disulfonic acid, containing 1000parts soda ash and 1800 parts tetrammine-cupri sulfate. Thesolutionturns a claret-red color and the coupling, which readily takesplace is soon finished. The dyestulf precipitates and is filtered off,Washed out and dried as usual. It is soluble in water with a bluish-redand in concentrated sulfuric acid with a violet color. It dyes cottonstrongly bluish-red shades of ver good fastnesls to light. It has mostproba ly the formu a:

(N OI (1 m):

wherein A stands for the disazo dyestufi' of the formula:

CHO OH 0H CH0 7 On N=N NH H018 0:11

This treatment with a cupri-ammine complex stabilizes in this particularcase the azo dyestufi? obtained from ortho-amino-benzaldehyde whichheretofore had only been possible by a treatment with hydroxylamine asdisclosed in the U. S. application Serial N 0. 74,163, filed by one ofus in conjunction with other inventors on Dec. 7, 1925. I

Similar dyestuffs are also obtained if 2- amino-1-hydroXy-benzcne or itsderivatives are substituted for the 2-amino-benzaldehyde of the examplesabove.

This is a division of our application Serial No. 153,723, filed onDecember 9, 1926.

We claim:

1. As a new\ product the complex cupriammine-azo dyestufi' of theprobable formula:

H (N113); III I Ill HI wherein A stands for the disazo dyestufi of theformula a How v which is soluble in water with a bluish-red color and inconcentrated sulfuric acid with a bluish-violet color" and which dyescotton Very fast bluish-red shades,

2.. Ks new products the complex cupriammine-azo dyestufls of theprobable generel formula:

wherein A represents a disazo dyestufli'imolecule containing inortho-position to each azo group a substituent of the group comprisingthe hydroxyl-, the carboxyl-, and the carbonyl groups, X representshydroxyl or a monovalent acid group, or both Xs together represent adivalent acid group, R represents a molecule of the ammonia type or ofthe aquo (H O) type, but at least one B being a molecule of the ammoniatype, and n represents the number 3 or 5. j

3., As new products the complex cupriammine-az'o dyestuffs of theprobable genral formula:

